DE68906234T2 - 2,2-Dimethyl-3- (1-hydroxy-2-sulfinoethyl) cyclopropane-carboxylic acid derivatives, process for their preparation and their use as pesticides. - Google Patents

Description

The present invention relates to new 2,2-dimethyl-3-(1-hydroxy-2-sulfino-ethyl)-cyclopropanecarboxylic acid derivatives, their preparation processes and their use as pesticides.

Derivatives of 3-[1-methylsulfonyloxy)ethyl]-2,2-dimethylcyclopropanecarboxylic acid are described in the European applications EP-A-269 514 and EP-A-217 342.

The invention relates to the compounds of formula (I) in all their possible isomer forms and isomer mixtures

wherein R₁ represents a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical having up to 8 carbon atoms, R₂ represents a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical having up to 8 carbon atoms or a saturated or unsaturated, linear, branched or cyclic acyl radical having up to 9 carbon atoms, X₁ and X₂, which are identical or different from one another, represent a fluorine, chlorine, bromine or iodine atom, a radical CF₃, CN, CO₂R, wherein R represents a linear alkyl radical having 1 to 8 carbon atoms, or a radical

where Hal represents a fluorine, chlorine or bromine atom, and R₃ represents a hydrogen atom, a saturated, linear alkyl radical having up to 8 carbon atoms or

- either a benzyl radical, optionally substituted by one or more radicals selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, alkenyl radicals having 2 to 6 carbon atoms, alkenyloxy radicals having 2 to 6 carbon atoms, alkadienyl radicals having 4 to 8 carbon atoms, methylenedioxy radicals and halogen atoms,

- or a group

wherein the substituent R" represents a hydrogen atom or a methyl radical and the substituent RA represents a monocyclic aryl radical or a group -C CH, and in particular a 5-benzyl-3-furylmethyl group,

- or a group

wherein a represents a hydrogen atom or a methyl radical and RB represents an aliphatic organic radical having 2 to 6 carbon atoms and one or more carbon-carbon unsaturations and in particular the radical -CH₂-CH=CH₂, -CH₂-CH=CH-CH₃, -CH₂-CH=CH-CH=CH₂, -CH₂CH=CH-CH₂-CH₃, -CH₂-C CH,

- or a group

wherein a and RB have the meaning given above, RC and RD, which are identical or different from each other, represent a hydrogen atom, a halogen atom, an alkyl radical having 1 to 6 carbon atoms, an aryl radical having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a cyano group,

- or a group

where B' represents an oxygen or sulphur atom, a group - - or -CH₂ or a sulphoxide group or a sulfone group and R₄ represents a hydrogen atom, a radical -CN, a methyl group, a radical -CONH₂, a radical -CSNH₂ or a radical -C CH, R₅ represents a hydrogen atom, a halogen atom or a methyl radical and n represents a number corresponding to 0, 1 or 2, and in particular the 3-phenoxybenzyl, α-cyano-3-phenoxybenzyl, α-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 1-(3-phenoxyphenyl)-ethyl or α-thioamido-3-phenoxybenzyl group,

- or a group

- or a group

wherein the substituents R₆, R₇, R₈ and R₆ represent a hydrogen atom, a chlorine atom or a methyl radical and wherein S/I symbolizes an aromatic ring or an analogous dihydro or tetrahydro ring,

- or a group

- or a group

wherein R₁₀ represents a hydrogen atom or a CN radical, R₁₂ represents a -CH₂- radical or an oxygen atom, R₁₁ represents a thiazolyl or thiadiazolyl radical whose bond with

can be located in any of the available positions, wherein R¹² is bonded to R¹¹ via the carbon atom located between the sulfur and a nitrogen atom,

- or a group

- or a group

wherein R₁₃ represents a hydrogen atom or a CN radical and W represents a hydrogen atom, a fluorine atom, a methyl radical or a methoxy group,

- or a group

wherein R₁₃ is as defined above and the benzoyl radical is bonded to the 3- or 4-positions of the phenyl radical,

- or a group

wherein R₁₄ represents a hydrogen atom, a methyl, ethynyl or cyano radical and R₁₅ and R₁₆, which are different from each other, represent a hydrogen atom, fluorine or bromine atom,

- or a group

wherein R₁₄ is as defined above, each of the R₁₇ radicals independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, 3,4-methylenedioxy, chlorine, fluorine or bromine p represents a number corresponding to 0, 1 or 2 and B" represents an oxygen or a sulfur atom,

- or a group

wherein R₁₈ represents a hydrogen atom, a methyl, ethynyl or cyano radical and R₁₉, differently, represents a hydrogen, fluorine or bromine atom and Ar represents an aryl radical having up to 14 carbon atoms,

- or a group

wherein the radicals Ar are as defined above.

Among the preferred compounds according to the invention there may be mentioned the compounds in which R₃ is a radical or those in which R₃ is a radical reproduces.

The compounds of formula I have several asymmetry centers, the carbons in the 1- and 3-position of the cyclopropane, the carbons in the 1'-position and the sulfur of the side chain

they can also have several asymmetric centers in the R3 part. The invention relates to the various possible stereoisomers as well as mixtures of these stereoisomers.

When R₁ or R₂; represents a hydrocarbon radical, it is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, a linear or branched alkyl radical which has a cyclic radical, or a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radical which is substituted by one or more alkyl radicals, e.g. the 1-methylcyclobutyl, 1-methylcyclopentyl, 1-methylcyclohexyl or 2,2,3,3-tetramethylcyclopropyl radical, or a vinyl or 1,1-dimethylallyl radical or an acetylenic radical, such as the ethynyl or propynyl radical.

If R₂ is an acyl radical, it is preferably the radical COCH₃, COC₂H₅, COC₆H₅ or COCH₂C₆H₅.

If X₁ or X₂ is a radical CO₂R, R preferably represents a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl radical.

If R₃ is an alkyl radical, it is preferably the methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl or tert-butyl radical.

The invention relates in particular to the compounds of formula I in which X₁ and X₂ each represent a bromine atom, those in which R₁ represents a hydrogen atom and those in which R₁ represents a methyl radical. Among the preferred compounds according to the invention, mention may be made of the compounds in which R₂ represents a COCH₃ radical and those in which R₂ represents a methyl radical. The invention relates in particular to the compounds of formula (I) in which the cyclopropane linkage has the 1R,cis structure.

Among the preferred compounds according to the invention, mention may be made in particular of the products whose preparation is given below in the experimental part.

The invention also relates to a process for preparing the compounds of formula I, which is characterized in that a compound of formula (II)

wherein X₁, X₂, R₂ and R₃ have the meaning given above and X₃ represents a chlorine, bromine or iodine atom, to the action of sodium dithionite in an aqueous medium to obtain the compound of formula IA corresponding to a product of formula (I) in which R₁ represents a hydrogen atom,

which is optionally subjected to the action of an etherifying agent capable of introducing the radical R'₁, where R'₁ has the meaning of R₁ with the exception of hydrogen, to give the compound of formula IB

corresponding to a product of formula (I) wherein R₁ is other than a hydrogen atom.

According to a preferred embodiment of the process of the invention, the compound of formula II and the sodium dithionite are reacted in the presence of water and a co-solvent to dissolve the product of formula II, e.g. in the presence of water and an alcohol such as methanol, or in the presence of water and tetrahydrofuran or dimethylformamide.

The compounds of formula II which are used as starting materials are generally known and are described in EP-A-269 514 and EP-A-217 342. Examples of preparations for the compounds of formula II can be found below in the experimental section. These preparations can be schematized as follows: R'₂ = R₂ with the exception of H R'₃ = R₃ with the exception of H

It is clear that one can first esterify the product III to obtain the product of the formula

after which the hydroxyl group is functionalized to obtain the product

to obtain.

The compounds of formula III are generally known and can be prepared by the process described in French Patent 2 396 006.

The compounds of formula (I) have interesting pesticidal properties: they are also soluble in water and can be used systemically to combat plant parasites. The compounds of formula I are used to combat parasites. This can, for example, involve combating plant parasites, parasites of premises and parasites of warm-blooded animals. The products according to the invention can thus be used to combat insects, nematodes and parasitic mites of plants and animals.

The invention thus relates to the use of the compounds of formula (I) in combating parasites of plants, parasites of premises and parasites of warm-blooded animals.

The products of formula (I) can therefore be used in particular for controlling insects in agriculture, for example for controlling lice, lepidopteran and coleopteran larvae. They are used in doses of between 10 g and 300 g of active ingredient per hectare.

The products of formula (I) can also be used to combat insects in premises, in particular to combat flies, mosquitoes and cockroaches.

The products of formula (I) can thus be used to combat parasitic mites on plants.

The compounds of formula (I) can also be used in the combat of parasitic nematodes of plants.

The compounds of formula (I) can also be used to combat parasitic mites of animals, for example to combat ticks and in particular ticks of the genus Boophilus, those of the genus Hyalomnia, those of the genus Amblyomnia and those of the genus Rhipicephalus, or to combat all species of scabies mites and in particular sarcoptic scabies, psoroptic scabies and chorioptic scabies.

The invention thus also relates to compositions for combating parasites of warm-blooded animals, parasites of premises and plants, which are characterized in that they contain at least one of the products defined above.

The invention relates in particular to insecticidal compositions containing as active ingredient at least one of the products defined above.

The compositions according to the invention are prepared according to conventional processes in the agrochemical industry or the veterinary industry or the industry of products intended for animal nutrition.

These compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, smoke bands, baits or other preparations commonly used in the use of this type of compounds.

In addition to the active ingredient, these compositions generally contain a carrier and/or a non-ionic surfactant which also ensures a uniform dispersion of the substances making up the mixture. The The carrier used may be a liquid such as water, alcohol, hydrocarbons or other organic solvents, a mineral oil, animal or vegetable oil, a powder such as talc, clays, silicates, diatomaceous earth, or a combustible solid.

The insecticidal compositions according to the invention preferably contain 0.005 to 10% by weight of active ingredient.

According to an advantageous embodiment for use in premises, the compositions according to the invention are used in the form of smoking compositions.

The compositions according to the invention can then advantageously consist, for the non-active part, of an insecticidal coil which is combustible or of a fibrous, non-combustible substrate. In this latter case, the fumigant obtained after introduction of the active ingredient is applied to a heating device such as an electric mosquito killer.

If an insecticidal snake is used, the inert carrier can consist of pyrethrum pulp, taboo powder (or powder from the needles of Machilus Thumbergii), pyrethrum stem powder, cedar needle powder, wood flour (such as sawdust), starch and coconut shell powder. The active ingredient dose can then be 0.03 to 1% by weight, for example.

If a non-flammable, fibrous carrier material is used, the active ingredient dose can then be, for example, 0.03 to 95 wt.%.

The compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on active ingredients, this oil impregnating the wick of a lamp and then subjecting it to combustion.

The concentration of the active ingredient incorporated into the oil is preferably 0.03 to 95% by weight.

The invention also relates to acaricidal compositions containing as active ingredient at least one of the products of formula (I) defined above.

The invention also relates to nematicidal compositions containing as active ingredient at least one of the products of the above formula (I).

The insecticidal compositions according to the invention, such as the acaricidal compositions, can optionally be mixed with one or more other pesticides. The acaricidal and nematicidal compositions can in particular be in the form of granules, suspensions, emulsions, solutions and powders.

For acaricidal use, it is preferable to use wettable powders for foliar spraying containing 1 to 80% of the active ingredient or liquids for foliar spraying containing 1 to 500 g/l of active ingredient. Powders for foliar spraying containing 0.05 to 3% of active ingredient can also be used.

For nematicidal use, it is preferable to use liquids for soil treatment that contain 300 to 500 g/l of active ingredient.

The acaricidal and nematicidal compositions according to the invention are preferably used in doses between 1 and 100 g of active ingredient/nectar.

The invention also relates to acaricidal compositions for combating parasitic mites of warm-blooded animals, in particular ticks and scabies mites, which are characterized in that they contain as active ingredient at least one of the products of formula (I) defined above.

When it comes to combating animal parasites, the compositions can be used in the form of sprays, baths or using the "pour-on" method.

If the pour-on method is used, solutions containing 0.5 to 4 g of active ingredient per 100 cc of solution are preferably used.

When it comes to combating parasitic mites on animals, the products according to the invention are very often incorporated into food compositions in association with a nutrient mixture adapted to the animal's diet. The nutrient mixture can vary according to the animal species, it can contain cereals, sugars and grains, soya, peanut and sunflower pomace, flours of animal origin, e.g. fish meal, synthetic amino acids, mineral salts, vitamins and antioxidants.

The invention also relates to compositions intended for animal nutrition which contain as active ingredient at least one of the products of formula (I) as defined above.

It can also be stated that the products according to the invention can be used as biocides or as growth regulators.

The invention also relates to associations with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active ingredient, on the one hand, at least one of the compounds of general formula (I) and, on the other hand, at least one of the pyrethrinoid esters chosen from the esters of allethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3-phenoxybenzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols of chrysanthemic acids, from the esters of 5-benzyl-3-furylmethyl alcohol of 2,2-dimethyl-3-(2-oxo-3,4,5,6-tetrahydrothiophenylidenemethyl)-cyclopropane-1-carboxylic acids, from the esters of 3-phenoxybenzyl alcohol and the α-cyano-3-phenoxybenzyl alcohols of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acids, among the esters of α-cyano-3-phenoxybenzyl alcohols of 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylic acids, among the esters of 3-phenoxybenzyl alcohol of 2-p-chlorophenyl-2-isopropylacetic acids, among the esters of allethrolones, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohols of 2,2-dimethyl-3-(1,2,2,2-tetrahaloethyl)-cyclopropane-1-carboxylic acids, in which "halo" represents a fluorine, chlorine or bromine atom, with the proviso that the compounds (I) can exist in all their possible stereoisomeric forms, as can the acidic linking components and alcohols of the above pyrethrinoid esters.

The associations according to the invention are of particular interest because they enable a wider range of parasites to be combated through the diversity of their action or because, in certain cases, they exhibit a synergistic effect.

To increase the biological activity of the products according to the invention, it is possible to add to them classic synergists used in similar cases, such as 1-(2,5,8-trioxadodecyl)-2-propyl-4,5-methylenedioxybenzene (or piperonyl butoxide) or N-(2-ethylheptyl)-bicyclo[2.2.1]-5-heptene-2,3-dicarboximide or piperonyl-bis-2-(2-n-butoxyethoxy)-ethyl acetal (or tropital).

The invention relates to pesticidal compositions as defined above, characterized in that they also contain a synergist of the pyrethrinoids.

example 1 Cyano-(3-phenoxyphenyl)-methyl-[1R-[1α-(S*),3α-(R*]]-3-[1- acetyloxy-2,2-dibromo-2-(methoxysulfinyl)-ethyl ]-2,2-dimethylcyclopropanecarboxylate

About 2.5 g of sodium dithionite dissolved in 100 ml of water are added to a solution of 7 g of the product prepared in Preparation 1 in 100 cc of methanol at 20ºC. 120 cc of methanol and 50 cc of tetrahydrofuran are added. The reaction mixture is stirred for 30 minutes at 20ºC. The solvents are evaporated under reduced pressure at 20-25ºC. The aqueous phase is acidified with a concentrated hydrochloric acid solution to obtain a pH of 1.5. The aqueous phase is saturated with sodium chloride and extracted with ethyl acetate. It is dried and concentrated under reduced pressure at 25ºC. The product obtained is dissolved in 50 cc of methylene chloride and add 80 cc of a solution of diazomethane in methylene chloride. The reaction mixture is then stirred for 1/4 hour at 25ºC and concentrated. The crude product obtained is purified by chromatography on silica, eluting with a hexane-isopropyl ether mixture (1/1). The residue is separated

the diastereomer A[α]D = -49º ± 1º (c=1%, CHCl₃)

the diastereomer B[α]D = +34.5º ± 1º (c=1%, CHCl₃).

Example 2 (3-Phenoxyphenyl)-cyanomethyl-1R-[1α-(S*),3α-(R* )]-2,2-dimethyl-3-[1-acetyloxy-2,2-dibromo-2-(hydroxysulfinyl)-ethyl]cyclopropanecarboxylate

Dissolve 2.96 g of the product prepared in preparation 1 in 30 cc of tetrahydrofuran, 10 cc of methanol and 10 cc of water at about 5°C; add a solution of 1 g of sodium dithionite in 10 cc of water. Allow to return to a temperature of 20°C and stir for 45 minutes at this temperature. Remove most of the solvents under reduced pressure at 20°C. Dilute with a little water to obtain a solution which is extracted with ethyl ether. Cool the aqueous phase to 0 ± 5°C, acidify with 14 mmol of hydrochloric acid and extract with ethyl ether. Dry this new ethereal phase, filter and concentrate under reduced pressure at 20°C. 1.58 g of the desired product are recovered.

Example 3 (3-Phenoxyphenyl)-methyl-1R-[1α,3α-(R*)]-2,2-dimethyl-3-[1- acetyloxy-2,2-dibromo-2-(hydroxysulfinyl)-ethyl]-cyclopropanecarboxylate

To a solution of 5.0 g of product prepared in Preparation 2 in a mixture of 80 cc of tetrahydrofuran and To 20 cc of water at 5ºC add 1.9 g of sodium dithionite dissolved in 10 cc of water. Allow the temperature to rise to about 20ºC and stir at this temperature for about 3/4 hour. Remove the tetrahydrofuran under reduced pressure at 20ºC. Dilute the residue with water to obtain a solution which is extracted with ethyl ether. Decant the aqueous phase, acidify with 20 mmol of hydrochloric acid and extract with ethyl ether. Dry, filter and evaporate to dryness under reduced pressure at 20ºC. 3.08 g of the desired product are obtained.

Example 4 (3-Phenoxyphenyl)-methyl-1R-[1α,3α-(R*)]-2,2-dimethyl-3-[1- methoxy-2,2-dibromo-2-(hydroxysulfinyl)-ethyl]-cyclopropanecarboxylate

Dissolve 2.95 g of 1R-cis-3-(2,2,2-tribromo-1R-methoxyethyl)-2,2-dimethylcyclopropanecarboxylic acid and 1.6 g of metaphenoxybenzyl alcohol in 50 cc of methylene chloride under magnetic stirring and under a nitrogen atmosphere. Add 0.2 g of dimethylaminopyridine and 1.65 g of dicyclohexylcarbodiimide at 0 ± 5°C; bring to 20°C and stir for 30 minutes. Remove insolubles by filtration. Concentrate the filtrate under reduced pressure at 40°C. Chromatograph on silica, eluting with a hexane-ethyl acetate mixture (95/5). 3.33 g of (3-phenoxyphenyl) methyl ester of the starting acid are thus obtained, which is dissolved in a mixture of 30 cc of tetrahydrofuran and 10 cc of methanol and 10 cc of water. 1.04 g of sodium dithionite dissolved in 10 cc of water are then added at 0 ± 5ºC. The temperature is allowed to rise to 20ºC and the mixture is stirred at this temperature for about 45 minutes. The solvents are removed under reduced pressure at 20ºC. The residue is diluted with water, cooled to 0 ± 5ºC and acidified to pH 1 with hydrochloric acid. and extracted with ethyl ether. The ethereal phase is dried, filtered and concentrated under reduced pressure at 20ºC. 2.12 g of the desired product are obtained.

Example 5 (3-Phenoxyphenyl)-cyanomethyl-1R-[1α-(S*),3α-(R* )]-2,2-dimethyl-3-[1-methoxy-2,2-dibromo-2-(hydroxysulfinyl)-ethyl]-cyclopropanecarboxylate

Dissolve 2.87 g of S-cyano-3-phenoxyphenyl)-methyl-1R-cis-3-(2,2,2-tribromo-1R-methoxyethyl)-2,2-dimethylcyclopropanecarboxylate in a solution of 25 cc of tetrahydrofuran, 20 cc of methanol and 10 cc of water, with magnetic stirring. Add a solution of 0.94 g of sodium dithionite in 8 cc of water, without exceeding 20°C. Stir the solution for 30 minutes at 20°C. Remove the methanol and tetrahydrofuran under reduced pressure. Dilute the residue with water and extract with ethyl ether. Decant the aqueous phase, cool to 0 ± 5°C and acidify with 10 mmol of hydrochloric acid. Extract with ethyl ether, dry, filter and concentrate under reduced pressure. This gives 2.35 g of the desired product.

Example 6 (3-Phenoxyphenyl)-cyanomethyl-1R-[1α-(S*),3α-(R* )]-2,2-dimethyl-3-(1-methoxy-2,2-dibromo-2-methoxysulfinylethyl)cyclopropanecarboxylate

Dissolve 2.52 g of the product prepared in Example 5 in 20 cc of methylene chloride. Add a solution of diazomethane in methylene chloride at 0 ± 5°C. Add 1 drop of acetic acid. Concentrate the solution under reduced pressure at 20°C. Chromatograph on silica eluting with 1,2-dichloroethane.

This yields 1.94 g of the desired product.

Production 1 S-Cyano-(3-phenoxyphenyl)-methyl-1R-cis-3-(2,2,2-tribromo-1R- acetoxyethyl)-2,2-dimethylcyclopropanecarboxylate Step A: 1R-cis-3-(2,2,2-tribromo-1R-acetoxyethyl)-2,2-dimethylcyclopropanecarboxylic acid

At -50°C, add a solution of 5.75 g of potassium tert-butoxide, 20 cc of tetrahydrofuran and 30 cc of tert-butyl alcohol to a solution of 10 g of 1R-cis-2,2-dimethyl-2-(1-hydroxy-2',2', 2'-tribromoethyl)-cyclopropanecarboxylic acid and 30 cc of tetrahydrofuran. Stir for 30 minutes at -50°C and add 2.4 cc of acetic anhydride. Stir and allow the temperature to rise again to -20°C. Stir for 50 hours at -20°C and pour the suspension into 2N hydrochloric acid. Extract with ethylene chloride, wash with water, dry and filter. Bring the filtrate to dryness. 9.7 g of product are recovered, which is poured into an aqueous sodium bicarbonate solution. The reaction mixture is stirred for 16 hours at 20°C. The crystals are filtered off and washed with water. The aqueous phase is acidified to pH 1 with hydrochloric acid. It is extracted with methylene chloride, washed with water, dried and filtered. The filtrate is brought to dryness. 3.3 g of the desired product are recovered, mp 178°C.

Step B: 3-Phenoxyphenylcyanomethyl-1R-[1≥-(S*),3≥-(R*)]- 2,2-dimethyl-3-[1-acetyloxy-2,2,2-tribromoethyl]cyclopropanecarboxylate

Dissolve 11.64 g of acid prepared in step A and 6 g of (S)-α-cyano-(3-phenoxy)-benzyl alcohol in 75 cc of methylene chloride at +10ºC. Add a solution of 5.5 g of dicyclohexylcarbodiimide, 0.32 g of dimethylaminopyridine in 50 cc of methylene chloride The mixture is brought to 20ºC and stirred for 18 hours. Insolubles are removed by filtration. The filtrate is concentrated under reduced pressure at 40ºC. The mixture is chromatographed on silica, eluting with a hexane-isopropyl ether mixture (7/3). 13 g of expected product are thus obtained.

Production 2 3-(Phenoxyphenyl)-methyl-1R-cis-3-(2,2,2-tribromo-1R-acetoxyethyl)-2,2-dimethylcyclopropanecarboxylate Step A: 3-(Phenoxyphenyl)methyl-1R-cis-3-(2,2,2-tribromo- 1R-hydroxyethyl)-2,2-dimethylcyclopropanecarboxylate

At 20°C, 10 g of 1R-cis-2,2-dimethyl-2-(1-hydroxy-2',2',2'-tribromoethyl)-cyclopropanecarboxylic acid are introduced into 200 cc of anhydrous benzene. The suspension is heated to benzene reflux and distilled to remove water. At the end of the distillation, it is brought to dryness under reduced pressure. A residue is obtained which is taken up in 40 cc of anhydrous dimethylformamide. The solution obtained is cooled to -60°C and 1.2 g of 50% sodium hydride is added. It is allowed to return to a temperature of 20°C. It is then stirred for 30 minutes at 20°C. 5.4 g of metaphenoxybenzyl chloride are added and the reaction mixture is stirred for 48 hours at 20°C. The suspension obtained is poured into 2N hydrochloric acid. It is stirred for 10 minutes and extracted with benzene. It is washed with water. It is dried and filtered. The filtrate is brought to dryness under reduced pressure. 14.5 g of product are recovered, which is chromatographed on silica eluting with a cyclohexane-ethyl acetate mixture (8/2). The product is recrystallized from isopropyl ether and petroleum ether (bp. 60-80°C). 10.35 g of the desired product are recovered, m.p. 50°C.

Step B: 3-(Phenoxyphenyl)methyl-1R-cis-3-(2,2,2-tribromo- 1R-acetoxyethyl)-2,2-dimethylcyclopropanecarboxylate

A solution of 1 g of the product prepared in step A, 2 cc of anhydrous pyridine and 2 cc of acetic anhydride is stirred for 2 days at 20°C. The solution is poured into 2N hydrochloric acid and stirred for 1 hour at 20°C. Extract with benzene. Wash the benzene solution with water. Dry the organic phase. Filter and bring to dryness. 0.782 g of the desired crude product is obtained, which is chromatographed on silica eluting with a cyclohexane-ethyl acetate mixture (9/1). The desired product is thus obtained.

Production 3 1R-cis-3-(2,2,2-tribromo-1R-methoxyethyl)-2,2-dimethylcyclopropanecarboxylic acid

At -20°C, add 5.75 g of potassium tert-butoxide, 20 cc of tetrahydrofuran and 30 cc of tert-butyl alcohol to a solution of 10 g of 1R-cis-2,2-dimethyl-2-(1-hydroxy-2',2',2'-tribromoethyl)-cyclopropanecarboxylic acid in 40 cc of tetrahydrofuran. Stir the reaction mixture for 30 minutes at -20°C and add 2.5 cc of methyl sulfate and 10 cc of tetrahydrofuran. Stir for 17 hours at -20°C. Pour into a mixture of water and hydrochloric acid. Stir for 10 minutes at 20°C; extract with ethyl ether and wash the organic phase with water until neutral. It is dried, filtered and the filtrate is brought to dryness under reduced pressure at 40ºC. The product obtained is recrystallized in benzene, filtered off with suction, the crystals obtained are washed and dried. 3.7 g of the desired product are obtained, mp 180ºC.

Production 4 3-Phenoxyphenyl-cyanomethyl-1R-[1α-(S*),3α-(R* )]-2,2-dimethyl-3-(1-methoxy-2,2,2-tribromethyl)-cyclopropanecarboxylate

Dissolve 7.1 g of acid prepared in preparation 3 and 4.5 g of (3-phenoxyphenyl)-(1S)-cyanomethyl alcohol in 100 cc of methylene chloride at 0 ± 5°C. Add 0.2 g of dimethylaminopyridine and 4.1 g of dicyclohexylcarbodiimide, bring back to 20°C and stir for 1 hour. Remove insolubles by filtration. The filtrate is concentrated under reduced pressure at 40°C. Chromatograph on silica, eluting with a hexane-ethyl acetate mixture (9/1). This gives 10.32 g of the desired product.

Example 7 Production of a soluble concentrate

A homogeneous mixture is made of

Product of Example 2 0.25 g

Piperonyl butoxide 1.00 g

Tween 80 0.25g

Topanol A 0.1 g

Water 98.4g

Example 8 Production of an emulsifiable concentrate

Mix intimately

Product of Example 3 0.015 g

Piperonyl butoxide 0.5 g

Topanol A 0.1 g

Tween 80 3.5g

Xylene 95.885 g

Example 9 Production of an emulsifiable concentrate

A homogeneous mixture is made of

Product of Example 4 1.5 g

Tween 80 20.0g

Topanol 0.1 g

Xylene 78.4 g

Example 10 Preparation of a smoking composition

Mix homogeneously

Product of Example 5 0.25 g

Taboo powder 25.00 g

Cedar needle powder 40.00 g

Pinewood flour 33.75 g

Brilliant Green 0.5 g

p-Nitrophenol 0.5 g

Biological investigation 1. Investigation of lethal activity in the housefly

The test insects are female houseflies aged 4 to 5 days. A topical nebulization of 1 microliter of acetone solution is performed on the dorsal thorax of the insects using an Arnold micromanipulator.

50 individuals are used per treatment. Mortality control is carried out 24 hours after treatment.

The results obtained, expressed in LD 50 or as the dose in nanograms per individual required to kill 50% of the insects, are the following. Compounds of Example LD 50 in ng/insect

Conclusion:

The products according to the invention have a very good lethal effect against houseflies.

2. Investigation of the lethal effect on larvae of Spodoptera littoralis

The tests are carried out by applying an acetone solution topically to the dorsal thorax of the larvae using the Arnold micromanipulator. 15 larvae are used per dose of the product to be tested. The larvae used are fourth instar larvae, i.e. approximately 10 days old, after having been reared at 24ºC and a relative humidity of 65%. After treatment, the individuals are transferred to an artificial nutrient medium (Poitout medium).

Mortality control is carried out 48 hours after treatment.

The obtained test results are given in the following table. Compounds of Example LD 50 in ng/insect

3. Investigation of the lethal effect against Aphis cracivora

Adult specimens are used after 7 days and 10 aphids are used for each concentration used. A contact ingestion method is used. Treatment is carried out using a Fisher gun on a bean leaf placed in a plastic Petri dish on a moistened paper pad. Treatment is carried out with 2 ml of acetone solution of the product to be tested (1 ml per leaf area). The insect is introduced after the leaf has dried. The insects are kept in contact with the leaf for 1 hour. The insects are placed on the untreated leaves and mortality is checked after 24 hours.

The obtained test results are given in the following table. Compound of Example LD 50 in mg/l

Claims (19)

1. In all their possible isomeric forms and mixtures of isomers, the compounds of formula (I) wherein R₁ represents a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical having up to 8 carbon atoms, R₂ represents a hydrogen atom, a saturated or unsaturated, linear, branched or cyclic hydrocarbon radical having up to 8 carbon atoms or a saturated or unsaturated, linear, branched or cyclic acyl radical having up to 9 carbon atoms, X₁ and X₂, which are identical or different from one another, represent a fluorine, chlorine, bromine or iodine atom, a radical CF₃, CN, CO₂R, wherein R represents a linear alkyl radical having 1 to 8 carbon atoms, or a radical where Hal represents a fluorine, chlorine or bromine atom, and R₃ represents a hydrogen atom, a saturated, linear alkyl radical having up to 8 carbon atoms or - either a benzyl radical, optionally substituted by one or more radicals selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, alkenyl radicals having 2 to 6 carbon atoms, alkenyloxy radicals having 2 to 6 carbon atoms, alkadienyl radicals having 4 to 8 carbon atoms, methylenedioxy radicals and halogen atoms, - or a group wherein the substituent R" represents a hydrogen atom or a methyl radical and the substituent RA represents a monocyclic aryl radical or a group -C CH, and in particular a 5-benzyl-3-furylmethyl group, - or a group wherein a represents a hydrogen atom or a methyl radical and RB represents an aliphatic organic radical having 2 to 6 carbon atoms and one or more carbon-carbon unsaturations and in particular the radical -CH₂-CH=CH₂, -CH₂-CH=CH-CH₃, -CH₂-CH=CH-CH=CH₂, -CH₂CH=CH-CH₂-CH₃, -CH₂-C CH, - or a group wherein a and RB have the meaning given above, RC and RD, which are identical or different from each other, represent a hydrogen atom, a halogen atom, an alkyl radical having 1 to 6 carbon atoms, an aryl radical having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or a cyano group, - or a group where B' represents an oxygen or sulphur atom, a group - - or -CH₂ or a sulphoxide group or a sulfone group and R₄ represents a hydrogen atom, a radical -CN, a methyl group, a radical -CONH₂, a radical -CSNH₂ or a radical -C CH, R₅ represents a hydrogen atom, a halogen atom or a methyl radical and n represents a number corresponding to 0, 1 or 2, and in particular the 3-phenoxybenzyl, α-cyano-3-phenoxybenzyl, α-ethynyl-3-phenoxybenzyl, 3-benzoylbenzyl, 1-(3-phenoxyphenyl)-ethyl or α-thioamido-3-phenoxybenzyl group, - or a group -or a group wherein the substituents R₆, R₇, R₈ and R₆ represent a hydrogen atom, a chlorine atom or a methyl radical and wherein S/I symbolizes an aromatic ring or an analogous dihydro or tetrahydro ring, - or a group - or a group wherein R₁₀ represents a hydrogen atom or a CN radical, R₁₂ represents a -CH₂- radical or an oxygen atom, R₁₁ represents a thiazolyl or thiadiazolyl radical whose bond with can be located in any of the available positions, wherein R₁₂ is bonded to R₁₁ via the carbon atom located between the sulfur and a nitrogen atom, - or a group - or a group wherein R₁₃ represents a hydrogen atom or a CN radical and W represents a hydrogen atom, a fluorine atom, a methyl radical or a methoxy group, - or a group wherein R₁₃ is as defined above and the benzoyl radical is bonded to the 3- or 4-positions of the phenyl radical, - or a group wherein R₁₄ represents a hydrogen atom, a methyl, ethynyl or cyano radical and R₁₅ and R₁₆, which are different from each other, represent a hydrogen atom, fluorine or bromine atom, - or a group wherein R₁₄ is as defined above, each of the R₁₇ radicals independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, 3,4-methylenedioxy, chlorine, fluorine or bromine p represents a number corresponding to 0, 1 or 2 and B" represents an oxygen or a sulfur atom, - or a group wherein R₁₈ represents a hydrogen atom, a methyl, ethynyl or cyano radical and R₁₉, differently, represents a hydrogen, fluorine or bromine atom and Ar represents an aryl radical having up to 14 carbon atoms, - or a group wherein the radicals Ar are as defined above. 2. Compounds of formula I as defined in claim 1 wherein X₁ and X₂ each represent a bromine atom. 3. Compounds of formula I as defined in claim 1 or 2, wherein R₁ represents a hydrogen atom. 4. Compounds of formula I as defined in claim 1 or 2, wherein R₁ represents a methyl radical. 5. Compounds of formula I as defined in any one of claims 1 to 4, wherein R₂ is a radical COCH₃. 6. Compounds of formula I as defined in any one of claims 1 to 4, wherein R2 is a methyl radical. 7. Compounds of formula I as defined in any one of claims 1 to 6, wherein the cyclopropane linkage has the 1R,cis structure. 8. Compounds of formula I as defined in claim 1, wherein R₃ is a radical reproduces. 9. Compounds of formula I as defined in claim 8, wherein R₃ is a radical means. 10. Process for the preparation of the compounds of formula I as defined in any one of claims 1 to 9, characterized in that a compound of formula (II) wherein X₁, X₂, R₂ and R₃ have the meaning given above and X₃ represents a chlorine, bromine or iodine atom, to the action of sodium dithionite in an aqueous medium to obtain the compound of formula 1A corresponding to a product of formula (I) in which R₁ represents a hydrogen atom, which is optionally subjected to the action of an etherifying agent capable of introducing the radical R'₁, where R'₁ has the meaning of R₁ with the exception of hydrogen, to give the compound of formula IB corresponding to a product of formula (I) wherein R₁ is other than a hydrogen atom. 11. Use of the compounds of formula I, as defined in any of claims 1 to 9, in combating parasites of plants and animals and parasites of premises. 12. Compositions for combating plant parasites, parasites of premises and parasites of warm-blooded animals, characterized in that they contain as active ingredient at least one of the products as defined in any one of claims 1 to 9. 13. Insecticidal compositions containing as active ingredient at least one of the products as defined in any one of claims 1 to 9. 14. Acaricidal compositions containing as active ingredient at least one of the products as defined in any one of claims 1 to 9. 15. Nematicidal compositions containing as active ingredient at least one of the products as defined in any one of claims 1 to 9. 16. Acaricidal compositions for combating parasites of warm-blooded animals, in particular ticks and scabies mites, characterized in that they contain as active ingredient at least one of the products as defined in one of claims 1 to 9. 17. Compositions for animal nutrition, containing as active ingredient at least one of the products as defined in any one of claims 1 to 9. 18. Associations with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active ingredient on the one hand at least one of the compounds of general formula (I) and on the other hand at least one of the pyrethrinoid esters selected from the esters of allethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohols of chrysanthemic acids, from the esters of 5-benzyl-3-furylmethyl alcohol of 2,2-dimethyl-3-(2-oxo-3,4,5,6-tetrahydrothiophenylidenemethyl)-cyclopropane-1-carboxylic acids, from the esters of 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohols of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acids, from the esters of α-cyano-3-phenoxybenzyl alcohol of 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylic acids, from the esters of 3-phenoxybenzyl alcohol, 2-p-chlorophenyl-2-isopropylacetic acids, from the esters of allethrolones, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohols, 2,2-dimethyl-3-(1,2,2,2-tetrahaloethyl)-cyclopropane-1-carboxylic acids, in which "halo" represents a fluorine, chlorine or bromine atom, with the proviso that the acidic linking components and the alcohols of the above pyrethrinoid esters can be present in all their possible stereoisomeric forms. 19. Compositions and associations according to one of claims 12 to 18, characterized in that they also contain a synergist of the pyrethrinoids.